New Synthetic Methods based on Fine Control with Iron Catalysts

• Project/Area Number: 25288018
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: URABE HIROKAZU 東京工業大学, 生命理工学研究科, 教授 (10176745)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2015: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2014: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2013: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000)
• Keywords: 共役付加反応 / グリニャール試薬 / 炭素―炭素多重結合 / 置換反応 / 低原子価鉄錯体 / 鉄塩 / 鉄触媒 / ハロゲン/メタル交換 / 共役付加

Outline of Final Research Achievements

This study reveals the following new synthetic reactions with iron catalysts (or reagents) and aryl Grignard reagents: addition of heterocycles to dienoates and related compounds / addition to dienylphosphine oxides / addition to dienylphosphonates / addition to substituted dienoates and related compounds / addition of aliphatic Grignard reagents to dienoates and related compounds / addition to ω-iododienoates and related compounds followed by cyclization / addition to enynoates and its application to a synthesis of meloscine / a 3-component coupling with enynoates and organic halides / preparation of cyclopropanes from ω-iododienoates, ω-iodoenoates, and related compounds / alkylation of pyridines at their 4-positions / synthetic study of zincophorin from functionalized diene monoepoxides / preparation of amines from nitro compounds / preparation of nitrones from nitro compounds, CeCl3, and CuF.

Research Products

• [Journal Article] Alkylation of Pyridines at Their 4-Positions with Styrenes plus Yttrium Reagent or Benzyl Grignard Reagents (2015)
  • Author(s): Tomoya Mizumori, Takeshi Hata, and Hirokazu Urabe
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 1 Pages: 422-426
  • DOI: 10.1002/chem.201404635
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Iron-Catalyzed Selective Conjugate Addition of Aryl Grignard Reagents to 2,4-Alkadienoates: tert-Butyl (Z)-5-Phenyl-3-hexenoate (2014)
  • Author(s): Takeshi Hata, Hideyuki Goto, Tomofumi Yokomizo, and Hirokazu Urabe
  • Journal Title: Org. Synth. Volume: 91 Pages: 307-321
  • DOI: 10.15227/orgsyn.091.0307
  • Peer Reviewed
• [Journal Article] Iron-Catalyzed Regio- and Stereoselective Conjugate Addition of Aryl Grignard Reagents to α,β,γ,δ-Unsaturated Sulfones and Its Synthetic Application (2013)
  • Author(s): Takeshi Hata, Takuya Nakada, Yun Taek Oh, Naoki Hirone, and Hirokazu Urabe
  • Journal Title: Advanced Synthesis & Catalyst Volume: 355 Issue: 9 Pages: 1736-1740
  • DOI: 10.1002/adsc.201201124
  • Peer Reviewed
• [Presentation] Selective Addition of Benzylzinc Reagents to Pyridines at Their 4-Positions (2015)
  • Author(s): Tomoya Mizumori, Kento Miyanaka, Takahiro Mitsui, Masayuki Shigeta, Takeshi Hata, and Hirokazu Urabe
  • Organizer: The Thirteenth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
  • Place of Presentation: Rihga Royal Hotel Kyoto (京都府京都市)
  • Year and Date: 2015-11-10
  • Int'l Joint Research
• [Presentation] ニトロ化合物とグリニャール試薬の還元的カップリング反応によるアミンおよびニトロンの選択的合成法の開発 (2015)
  • Author(s): 秦 猛志、辰巳湧太、田中直美、重田雅之、占部弘和
  • Organizer: 第107回有機合成シンポジウム
  • Place of Presentation: 慶應義塾大学薬学部(東京都港区)
  • Year and Date: 2015-06-09
• [Presentation] Fe触媒によるグリニャール試薬のエンイノエート類への選択的な1,6-付加反応とmeloscineの合成研究 (2015)
  • Author(s): 大谷彗介、岩田智史、重田雅之、秦 猛志、占部弘和
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス・薬学部
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 鉄触媒によるシクロプロピルグリニャール試薬の2,4-アルカジエノエートまたはアミドへの立体選択的1,6-付加反応 (2015)
  • Author(s): 菅野剛志、水野 瞳、重田雅之、秦 猛志、占部弘和
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス・薬学部
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Fe触媒によるグリニャール試薬とω-ハロ-α,β,γ,δ-不飽和エステル・アミドの付加・環化を経たワンポット立体選択的シクロペンタンおよびヘキサン合成 (2015)
  • Author(s): 中川一茂、成相 智、秦 猛志、占部弘和
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス・薬学部
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Synthetic Studies of (+)-Zincophorin by the Repeated Use of Iron-Catalyzed Methylation (2015)
  • Author(s): KWEK, Cheah Ming、後藤英之、重田雅之、秦 猛志、占部弘和
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス・薬学部
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] グリニャール/Ce/Cu三元試薬によるニトロ化合物からニトロンの合成 (2015)
  • Author(s): 辰巳湧太、田中直美、秦 猛志、占部弘和
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス・薬学部
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] ピリジン4位へのベンジル亜鉛試薬の位置選択的付加反応 (2015)
  • Author(s): 水森智也、三井崇裕、宮仲健人、重田雅之、秦 猛志、占部弘和
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス・薬学部
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] スチレンとイットリウム試薬またはベンジルグリニャール試薬によるピリジンの4位選択的置換反応 (2014)
  • Author(s): 水森智也、宮仲健人、三井崇裕、秦 猛志、占部弘和
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学 (福岡県・福岡市)
  • Year and Date: 2014-09-23 – 2014-09-25
• [Presentation] 鉄触媒存在下ニトロ化合物とグリニャール試薬の還元的カップリング反応によるアミン合成 (2013)
  • Author(s): 秦 猛志、辰巳湧太、占部弘和
  • Organizer: 第60回有機金属化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] Copper- or Iron-Mediated Three-component Coupling of 2-Alken-4-ynoates, Grignard Reagents, and Organic Halides (2013)
  • Author(s): Iwata. S.; Ohtani, K.; Hata, T.; Urabe, H.
  • Organizer: 10th International Symposium on Carbanion Chemistry (ISCC-10)
  • Place of Presentation: 京都
• [Presentation] Iron-catalyzed Selective Addition of Aryl Grignard Reagents to Electron-Deficient Dienes (2013)
  • Author(s): Nakagawa, K.; Oh, Y. T.; Hata, T.; Urabe, H.
  • Organizer: 10th International Symposium on Carbanion Chemistry (ISCC-10)
  • Place of Presentation: 京都